Electrochemical cell with improved high-rate discharge performance

ABSTRACT

An alkaline electrochemical cell has a central cathode having a corresponding cathode current collector electrically connected with a positive terminal of the electrochemical cell. The cathode current collector has a tubular shape, such as a cylindrical shape or rectangular shape, extending parallel with the length of the central cathode. The cathode current collector is embedded within the central cathode, such as at a medial point of a radius of the central cathode, thereby minimizing the distance between the cathode current collector and any portion of the central cathode, thereby increasing the mechanical strength of the cathode and facilitating charge transfer to the cathode current collector.

CROSS-REFERENCE TO RELATED APPLICATIONS

This patent application is a divisional of U.S. patent application Ser.No. 16/455,124, filed Jun. 27, 2019, which is a continuation of U.S.patent application Ser. No. 16/454,991, filed Jun. 27, 2019, each ofwhich is incorporated herein by reference in its entirety.

BACKGROUND

Batteries in the form of electrochemical cells are used as power sourcesfor a wide range of electronic devices. The requirements of thoseelectronic devices are important factors in battery design. For example,many electronic devices have battery compartments that limit the sizeand/or shape of batteries to be contained therein. Thus, certainelectrochemical cells, such as alkaline primary batteries, arecommercially available in cell sizes commonly known as LR6 (AA), LR03(AAA), LR14 (C) and LR20 (D). The cells have a cylindrical shape thatmust comply with the dimensional standards that are set by organizationssuch as the International Electrotechnical Commission. Moreover, thedischarge characteristics of the batteries should be provided toaccommodate the intended device operation under expected conditions ofuse.

Over time, many electronic devices have incorporated increasing numbersof features that require higher-power draws from onboard batteries toappropriately power the devices. The increased high-power demands ofthese electronic devices require batteries capable of deliveringconsistent high-rate discharge performance over an extended period oftime. However, high-rate discharge of traditional battery chemistries,such as traditional alkaline batteries incorporating manganese dioxidecathode materials and zinc-based anode materials within an alkalineelectrolyte solution, often results in decreases in dischargeefficiency, with a battery often failing to deliver desired voltageoutputs well before all of the active material within the battery isexhausted.

Accordingly, a need constantly exists for improvements in battery designto improve discharge performance under various discharge ratecircumstances.

BRIEF SUMMARY

Certain embodiments are directed to an alkaline electrochemical cellhaving a centrally-located, cathode, surrounded by an anode, wherein thecathode is separated from the anode by a separator. The cathode has anassociated tubular (e.g., cylindrical or rectangular) mesh currentcollector extending along at least a portion of the length of thecathode, and electrically connecting the cathode to a positive contactterminal.

Various embodiments are directed to an alkaline electrochemical cellcomprising: a container; and an anode ring positioned within thecontainer and defining an opening therein, wherein the anode ringcomprises a zinc active material; an inner cathode positioned within theopening of the anode, wherein the inner cathode comprises a manganeseoxide active material; a cathode current collector comprising aconducting tube positioned within the inner cathode, wherein the cathodecurrent collector is electrically connected with a positive terminal ofthe electrochemical cell; and a separator positioned between the anodering and the inner cathode.

In certain embodiments, the alkaline cell further comprises an outercathode ring positioned between an outer surface of the anode ring andan interior surface of the container. In various embodiments, thecathode current collector is in electrical contact with the containervia a conductive tab. In certain embodiments, the conducting tubecomprises a conducting mesh material. Moreover, the conducting tube maycomprise a nickel mesh material. In various embodiments, the nickel meshmaterial has a graphite coating. In certain embodiments, the conductingtube comprises a perforated nickel foil material. In variousembodiments, the conducting tube comprises a conducting wire coil.Moreover, the cathode current collector may have a cross-sectional shapecorresponding to the shape of the inner cathode. In certain embodiments,the inner cathode has a cylindrical shape, and a diameter of the cathodecurrent collector is at least substantially half of a diameter of theinner cathode. In various embodiments, the cathode current collector isembedded within an exterior surface of the inner cathode. In certainembodiments, the inner cathode comprises a plurality of cylindricalcathode pellets stacked axially within the opening of the anode.Moreover, the cathode current collector may be embedded within anexterior surface of each of the plurality of cylindrical cathodepellets. In various embodiments, the anode ring comprises a gelledanode.

Various embodiments are directed to an alkaline electrochemical cellcomprising: a container; an outer cathode ring positioned adjacent aninterior surface of the container and defining an opening therein,wherein the outer cathode ring comprises a cathode active material; atleast one anode portion positioned within the opening of the outercathode, wherein the at least one anode comprises a zinc activematerial; an inner cathode positioned adjacent a side of the at leastone anode portion; a cathode current collector comprising a conductingtube positioned within the inner cathode, wherein the cathode currentcollector is electrically connected with a positive terminal of theelectrochemical cell; and a separator material: positioned between theouter cathode ring and the at least one anode portion; and positionedbetween the at least one anode portion and the inner cathode.

In various embodiments, the cathode current collector is in electricalcontact with container via a conductive tab. In certain embodiments, theconducting tube comprises a conducting mesh material. In variousembodiments, the inner cathode has an at least substantially rectangularcross-section. Moreover, the at least one anode portion comprises twoanode portions, wherein the two anode portions are positioned onopposite sides of the inner cathode. In certain embodiments, the cathodecurrent collector has a cross-sectional shape corresponding to thecross-sectional shape of the inner cathode. In various embodiments, thecathode current collector is embedded within an exterior surface of theinner cathode. In various embodiments, the cathode comprises: a cathoderod comprising a cathode active material; and a cathode currentcollector comprising a conducting tube embedded within the cathode rod.Moreover, the cathode rod may be a cylinder. The cathode rod maycomprise a plurality of cathode pellets stacked axially relative to oneanother. In certain embodiments, the cathode current collector iswrapped around the plurality of cathode pellets and embedded within anouter surface of the plurality of cathode pellets. In variousembodiments, the cathode current collector has a shape corresponding tothe shape of the cathode rod. In certain embodiments, the cathode rodand the cathode current collector are at least substantially cylindricaland the cathode current collector is at least substantially concentricwith the cathode rod, and wherein the cathode current collector has adiameter at least substantially half of a diameter of the cathode rod.Moreover, the cathode rod and the cathode current collector are at leastsubstantially rectangular. In certain embodiments, the conducting tubecomprises a conducting mesh or perforated material. Moreover, theconducting tube may comprise a nickel mesh material. In certainembodiments, the nickel mesh material has a graphite coating. In variousembodiments, the conducting tube comprises a perforated nickel foilmaterial. Moreover, the conducting tube may comprise a conducting wirecoil.

Certain embodiments are directed to a method of manufacturing anelectrochemical cell, the method comprising: placing an outer cathodering within a container, wherein the outer cathode ring is in contactwith an interior surface of the container and defines a cathode openingbounded by an inner surface of the outer cathode ring; covering theinner surface of the outer cathode ring with a separator material;disposing an anode material within the cathode opening, wherein theanode material is separated from the container and the outer cathodering by the separator; positioning an inner cathode comprising anembedded cathode current collector and covered with a separator withinthe cathode opening of the outer cathode ring, thereby displacing atleast a portion of the anode material into a gap defined between theinner surface of the outer cathode ring and an outer surface of theinner cathode; electrically connecting the cathode current collectorwith the container; extending an anode current collector into the anodematerial; and sealing the container with a cover, wherein the cover isin electrical connection with the anode current collector.

In various embodiments, electrically connecting the cathode currentcollector with the container comprises attaching a conducting tabbetween the cathode current collector and the container. Moreover, themethod may further comprise electrically insulating the conducting tabfrom the anode and anode current collector. In certain embodiments,positioning an inner cathode within the cathode opening furthercomprises: forming a plurality of cathode pellets; stacking theplurality of cathode pellets axially; embedding the cathode currentcollector within an exterior surface of the plurality of cathode pelletsto form the inner cathode; and wrapping the inner cathode with theseparator material.

Certain embodiments are directed to a method of manufacturing anelectrochemical cell, wherein the method may comprise: placing an outercathode ring within a container, wherein the outer cathode ring is incontact with an interior surface of the container and defines a cathodeopening bounded by an inner surface of the outer cathode ring; coveringthe inner surface of the outer cathode ring with a separator material;positioning an inner cathode comprising an embedded cathode currentcollector and covered with a separator within the cathode opening of theouter cathode ring such that an outer surface of the inner cathode isspaced apart from the inner surface of the outer cathode ring; disposingan anode material between the outer cathode and the inner cathode;electrically connecting the cathode current collector with thecontainer; extending an anode current collector into the anode material;and sealing the container with a cover, wherein the cover is inelectrical connection with the anode current collector.

In certain embodiments, electrically connecting the cathode currentcollector with the container comprises attaching a conducting platebetween the cathode current collector and a closed bottom end of thecontainer. In various embodiments, electrically insulating theconducting plate from the anode. Moreover, positioning an inner cathodewithin the cathode opening may further comprise: forming a plurality ofcathode pellets; stacking the plurality of cathode pellets axially;embedding the cathode current collector within an exterior surface ofthe plurality of cathode pellets to form the inner cathode; and wrappingthe inner cathode with the separator material.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

Reference will now be made to the accompanying drawings, which are notnecessarily drawn to scale, and wherein:

FIG. 1 shows a cross-sectional view of a conventional battery cell takenalong the longitudinal axis of the cell;

FIG. 2 is a cross-sectional view of the battery cell in FIG. 1 , takenperpendicular to the longitudinal axis of the cell, at II-II;

FIG. 3 shows a cross-sectional view of a battery according to variousembodiments, taken along the longitudinal axis of the cell;

FIG. 4 shows a cross-sectional view of another battery according tovarious embodiments, taken along the longitudinal axis of the cell;

FIG. 5 is a cross-sectional view of the battery cell in FIG. 3 , takenperpendicular to the longitudinal axis of the cell at III-III;

FIG. 6 shows a cross-sectional view of another battery according tovarious embodiments, taken along the longitudinal axis of the cell;

FIG. 7 is a cross-sectional view of the battery cell in FIG. 6 , takenperpendicular to the longitudinal axis of the cell at IV-IV;

FIG. 8 is a cross-sectional view of another battery according to variousembodiments, taken perpendicular to the longitudinal axis of the cell;

FIG. 9 is a cross-sectional view of another battery according to variousembodiments, taken perpendicular to the longitudinal axis of the cell;

FIG. 10 shows graphical discharge charts for an experimental cellconfigured in accordance with FIG. 3 compared with reference cells;

FIG. 11 shows a cross-sectional view of another battery according tovarious embodiments, taken along the longitudinal axis of the cell.

DETAILED DESCRIPTION

The present disclosure more fully describes various embodiments withreference to the accompanying drawings. It should be understood thatsome, but not all embodiments are shown and described herein. Indeed,the embodiments may take many different forms, and accordingly thisdisclosure should not be construed as limited to the embodiments setforth herein. Rather, these embodiments are provided so that thisdisclosure will satisfy applicable legal requirements. Like numbersrefer to like elements throughout.

Referring to FIG. 1 , a conventional primary alkaline electrochemicalbattery cell 10 is shown. Cell 10 includes a housing, comprising a canwith a side wall 12, a closed bottom end 14, and an open top end 16. Apositive terminal cover 18 is welded or otherwise attached to can bottom14. Alternatively, can bottom 14 may be formed to include the shape ofpositive terminal cover 18 in order to function as the positive terminaland eliminate the need for a separate cover. Assembled to the open topend 16 of the can is a cover and seal assembly and a negative terminalcover 30. A plastic film label 20 or other jacket may be formed aboutthe exterior surface of the can side wall 12. Label 20 may extend overthe peripheral edges of positive and negative terminal covers 18 and 30.A positive electrode (cathode) 22 is formed about the interior surfaceof the can. Cathode 22 is in direct contact with a portion of the can,and the can functions as the cathode current collector, providingelectrical contact between cathode 22 and positive terminal cover 18. Anegative electrode (anode) 26 is disposed within a cavity in cathode 22,with a separator 24 between cathode 22 and anode 26. A layer ofseparator 38 is also disposed between the anode 26 and the can bottom14. An anode current collector 28 extends from negative terminal cover30 into anode 26 to provide electrical contact between anode 26 andcover 30. An annular seal 32 is disposed in the open end 16 of the canto contain the electrode materials and electrolyte in the can. An innercover 34 provides compressive support for seal 32 to achieve the desiredlevel of resistance to leakage of materials from cell 10. Seal 32 alsoelectrically insulates negative terminal cover 30 from the side wall 12of the can. The cathode 22 and the anode 26 are coaxially disposed withrespect to each other, sharing the longitudinal axis 36 of the cell 10as a common axis.

FIG. 2 is cross-sectional view of the cell 10 in FIG. 1 taken at II-II.Cathode 22 has a hollow circular cylindrical shape with an internalsurface that is generally smooth. The external surface of cathode 22conforms generally to the shape of the internal surface of can side wall12. The external surface of cathode 22 may be in direct contact with canside wall 12. Cathode 22 also has an internal surface, which defines acavity. Anode 26 is disposed within the cylindrical cavity defined bythe internal surface of cathode 22. Separator 24 is disposed betweencathode 22 and anode 26.

Example embodiments of a cell are shown in FIGS. 3-4 . Cells 110 ofFIGS. 3-4 constitute alkaline, Zinc-Manganese Dioxide (e.g.,electrolytic Manganese Dioxide (EMD)) cells. The cell 110 comprises anouter cylindrical container having a closed end and an opposite open end116, which may be defined as a can having sidewalls 112 and a can bottom114 (which may itself define a terminal cover of the battery, such as apositive terminal cover, or which may have a separate terminal cover 115attached (e.g., welded) thereto). The can may be embodied as a steelcan, plated on its exterior surface with nickel. The open end 116 of thecell may be closed with an annular seal 132 comprising a polymericmaterial, such as nylon, polyethylene, polypropylene, and/or the like.In certain embodiments, the annular seal 132 may define a pressurerelief vent configured to rupture if the cell's internal pressurebecomes excessive. The cell may also comprise a cover 130 (e.g., metalcover) disposed in the open end 116 of the cell such that, when the topedge of the can is crimped inward and/or reduced in diameter, the cover130 cooperates with the annular seal 132 and the can to compressivelyseal the electrodes and electrolyte in the cell 110. Moreover, the cover130 may operate as a terminal cover (e.g., a negative terminal cover) ofthe cell 110. Cell components that may be exposed to the electrodes orelectrolyte comprise materials that are nonreactive with the electrodematerials and/or the electrolyte under expected conditions of cellstorage and use. The cell can may define a pressure relief vent, whichmay be disposed in the seal, a cell cover, a can wall, and/or the like.Each electrode has a current collector to make electrical connectionbetween the electrode and a respective cell contact terminal. The canmay serve as a current collector for one electrode (e.g., cathode 122 i,122 o), such as the electrode formed against the inner surface of thecan sidewalls 112, in which case a coating containing carbon (e.g.,graphite) may be applied to the interior surface of the can side wall112 to improve electrical contact with the electrode (e.g., inembodiments such as those shown in FIG. 3 , where a cathode 122 oembodies the outermost electrode of the cell). However, it should beunderstood that in embodiments in which the effective surface area ofthe current collector of an electrode in contact with the can isdesirably minimized (such as where an anode 226 o is an outermostelectrode of the cell, as shown in FIG. 11 ), at least a portion of theinterior surface of the can side wall 112 may be coated with aninsulating material to control the effective size of the currentcollector, as embodied by the can side wall 112.

Alternatively, the outer electrode may be electrically insulated fromthe can and may have a separate current collector (not shown). The cell110 may also comprise one or more cell covers (e.g., positive terminalcover 115) that may serve as cell contact terminals. At least one ofthese cell contact terminals may be in electrical connection with thecell can (e.g., by welding the cell contact terminal 115 onto theexterior surface of the closed end 114 of the cell can). However, itshould be understood that a portion of the can itself may define a cellcontact terminal. For example, the closed end of the can may be formedin the shape of a contact terminal, thereby eliminating the need for aseparate cover. Others of these cell contact terminals may beelectrically insulated from the can (e.g., the negative terminal cover,embodied as outer cover 130 may be insulated from the positively-chargedcan by the above-mentioned annular seal 132) thereby enabling opposingends of the battery cell 110 to have opposite electrical polarity of thebattery cell 110, without short circuits defined therebetween.

In contrast to the cell 10 shown in FIGS. 1-2 , Cell 110 of FIG. 3includes a plurality of cathode layers, including an outer, ring-shapedcathode 122 o and an inner cylindrical cathode 122 i. The outer cathode122 o of the illustrated embodiment is disposed adjacent an interiorsurface of the can side wall 112 and surrounding an exterior surface ofan annular anode 126 (separated by one or more separator 124 layers),which itself surrounds an exterior surface of an inner, cylindricalcathode 122 i (separated by one or more separator 124 layers). Outercathode 122 o has a hollow, circular and cylindrical shape with aninternal surface that is generally smooth. The external surface of thecathode 122 o conforms generally to the shape of the internal surface ofthe can side wall 112. At least a portion of the external surface of thecathode 122 o may be in direct contact with the can sidewall 112,thereby utilizing the can side wall 112 as a current collector for thecathode 122 o. By utilizing the can side wall 112 as the currentcollector for the outer cathode 122 o (the electrode locate adjacent tothe can side wall 112), the cell design may minimize inactive materialsin the form of a separate cathode current collector, which wouldotherwise occupy volume within the cell 110 that could otherwise beoccupied by active materials

The annular anode 126 is positioned between the outer cathode 122 o andinner cathode 122 i (separated from each by one or more separator 124layers). As shown in FIG. 3 , the annular anode 126 utilizes an anodecurrent collector 127, which may be embodied as a nail extending fromthe negative terminal cover into the anode 126. The anode currentcollector 127 may be at least substantially linear, extending from thenegative terminal cover 130 into the anode 126. However, in otherembodiments the anode current collector 127 may be non-linear, such thatthe anode current collector 127 extends from a centerpoint of thenegative terminal cover 130 (which is aligned with a central axis of thecell 110) into a portion of the anode 126, which itself is spaced apartfrom the center axis of the cell 110.

Because the inner cathode 122 i is not in direct contact with theinterior surface of the can side wall 12, the cell 110 has a separatecurrent collector 128 corresponding with the inner cathode 122 i. Thecurrent collector 128 comprises a material high in electricalconductivity, with sufficient strength and/or ductility to withstand thecell manufacturing process, and that is physically and chemically stablein the internal cell environment under expected conditions of storageand use. Materials suitable for use as cathode current collectors 128 invarious embodiments comprise metal materials, such as steel, stainlesssteel, nickel, and/or alloys thereof. Such materials may be coated toprovide additional conductive characteristics and/or to improve contactbetween the cathode current collector 128 and the cathode 122 i. As justone example, a cathode current collector 128 may comprise a nickel meshcoated with graphite. As another example, the cathode current collector128 may comprise a perforated nickel foil (e.g., coated with graphite).Other conductive materials may also be used (e.g., in the alternative orin combination), such as electrically conductive plastics, plasticshaving embedded conductive materials, and/or the like.

In the illustrated embodiment, the cathode current collector 128comprises a cylindrical mesh extending longitudinally along the lengthof the inner cathode 122 i. It should be understood that otherconfigurations may be alternatively suitable, such as perforated sheets,expanded sheets, grids, crossed-wire sheets, and/or the like.

As shown in FIGS. 3-4 , the cylindrical cathode current collector 128may be embedded within the interior of the inner cathode 122 i, suchthat the cathode current collector 128 is positioned at approximatelythe mid-point of a radius of the inner cathode 122 i (e.g., such thatthe mesh current collector 128 is at least approximately equidistantbetween the central axis of the inner cathode 122 i and the outersurface of the inner cathode 122 i). In other words, the cathode currentcollector 128 may have a radius that is at least substantially half ofthe radius of the cathode 122, and both the cathode current collector128 and the inner cathode 122 i may have a central axis aligned with thelongitudinal axis of the cell 110. As just one non-limiting example, fora LR6 battery, the inner cathode 122 i may have a length of at leastapproximately 1.6 inches and a diameter of at least approximately 0.189inches, and the embedded cathode current collector 128 may be formed byrolling a flat mesh around a round forming die having a diameter of 2 mm(approximately 0.0787 inches) to form a cathode current collector 128having a diameter of approximately 0.0787 inches for inclusion withinthe inner cathode 122 i.

It is thought that minimizing the distance between any portion of thecathode (e.g., inner cathode 122 i) and the cathode current collector128 with the foregoing configuration increases performances of the cell110, possibly by decreasing the contact resistance between the collectorand the cathode.

The cathode current collector 128 is electrically connected with the canside walls 112 (which operate as the current collector for the outercathode 122 o) via a conducting member. In the illustrated embodiment ofFIG. 3 , for example, the conducting member is embodied as a conductingtab 141 (e.g., a thin flat conducting strip, a conducting wire, and/orthe like) electrically connected with the cathode current collector 128(e.g., by welding) and electrically connected with the can side walls112 (e.g., by welding). To electrically connect the cathode currentcollector 128 with the can side walls 112, the conducting tab passesacross the top of the anode 126 ring, thereby electrically coupling thetwo cathode portions 122 i, 122 o. To ensure the positively chargedconducting tab 141 remains electrically insulated from the negativelycharged anode 126 and negatively charged anode current collector 127(thereby avoiding a short-circuit scenario) insulating plates 134, 135may be positioned below and above the conducting tab 141. The insulatingplates 134, 135 may comprise an electrically insulating material (e.g.,a nylon, a plastic, and/or the like) and the insulating plates may beconfigured so as to prevent undesired contact between the conducting tab141 and any negatively charged portions of the cell 110. As shown, alower insulating plate 134 may comprise an aperture aligned with aninner cathode 122 i, thereby enabling the conducting tab 141 to exit atop surface of the inner cathode 122 i so as to pass over the anode 126and to contact a can side wall 112. The lower insulating plate 134 mayadditionally comprise a separate aperture enabling the anode currentcollector 127 to pass through the lower insulating plate 134 into theanode at a position spaced away from the conducting tab 141. Moreover,an upper insulating plate 135 is positioned between the conducting tab141 and the anode current collector 127. As illustrated, the upperinsulating plate 135 defines a single aperture enabling the anodecurrent collector 127 to pass therethrough.

In other embodiments, such as that shown in FIG. 4 , the conductingmember may be embodied as a conducting plate 142 electrically connectedwith (e.g., welded) a bottom end of the cathode current collector 128and electrically connected with an interior surface of the closed bottomend 114 of the cell can. In such embodiments, the anode 126 may beinsulated from the cathode conducting plate 142 via a bottom cup 125(e.g., comprising a separator material or another insulating material)preventing contact between the anode 126 and the cathode conductingplate 142. An analogous bottom cup may be utilized in the configurationdiscussed in reference to FIG. 3 .

In other embodiments, such as those shown in FIG. 6 , the cathodecurrent collector 128 may be located at the exterior surface of theinner cathode 122 i. However, it should be understood that thecylindrical cathode current collector 128 may be located at otherlocations along the radius of the inner cathode 122 i. Moreover, in anyof these embodiments, the cathode current collector 128 is electricallyconnected with the can side walls 112 via a conducting member, such as aconducting tab 141 and/or a conducting plate 142, as discussed inreference to FIGS. 3-4 .

In yet other embodiments, the cathode current collector 128 may haveother configurations. For example, the cathode current collector 128 maybe defined as a coil-type current collector defined as a conductive wirecoil having a spring-shape extending along the length of the innercathode 122 i. In such embodiments, the coil-type current collectorextends at least partially along a length of the inner cathode 122 i,and may be concentric with the inner cathode 122 i (and the cell 110).In certain embodiments, the coil-type current collector may have aradius that is at least substantially half of the radius of the innercathode 122 i. However, it should be understood that the coil-typecurrent collector may have other diameters, such as having a diameter atleast substantially equal to the diameter of the inner cathode 122 i,such that the coil-type current collector is embedded at the outersurface of the inner cathode 122 i.

In yet other embodiments, the cathode current collector 128 may haveother, non-cylindrical configurations. For example, the cathode currentcollector 128 may have an oblong cross-sectional shape (the center ofwhich may be aligned with a central axis of the inner cathode 122 i andthe longitudinal axis 136 of the cell 110), a flat cross-section (thecenter of which may be aligned with a central axis/plane of the innercathode 122 i), a rectangular cross-section (the center of which may bealigned with a central axis of the inner cathode 122 i), a solid centralpin current collector (positioned concentric with the inner cathode 122i), and/or the like.

For example, FIGS. 8-9 illustrate cross-sectional views of alternativecell configurations in accordance with certain embodiments. As showntherein, the outer cathode 122 o surrounds a plurality of anode portions126 (e.g., two anode portions 126 in the shown embodiments of FIGS. 8-9) positioned on opposing sides of the inner cathode 122 i. As shown inthe illustrated embodiment, the outer cathode 122 o has a cylindricalconfiguration with a cylindrical interior opening. The plurality ofanode portions 126 have an outer surface contoured with a portion of theinterior surface of the outer cathode 122 o and contoured to an outersurface of an at least substantially rectangular inner cathode 122 i.Such a configuration gives the anode portions 126 a “D”-shape, having anat least substantially linear side and an at least substantially curvedside. The anode portions 126 are separated from the outer cathode 122 oand the inner cathode 122 i by one or more separator 124 layers. In theillustrated embodiment, the separator 124 positioned between the outercathode 122 o and the anode portions 126 may extend around the entiretyof the interior surface of the outer cathode 122 o. In such embodiments,an exterior surface of the inner cathode 122 i may be surrounded by aseparator 124 to separate the inner cathode 122 i from the separatorportions 126. In other embodiments, the separator 124 may extend aroundeach individual anode portion 126, thereby separating the anode portions126 from each of the inner cathode 122 i and outer cathode 122 o, whichmaintains electrical contact between the outer cathode 122 o and innercathode 122 i.

In the illustrated embodiments of FIGS. 8-9 , the anode portions 126 mayeach have associated anode current collectors 127, which may be embodiedas individual nails extending between a negative terminal cover andrespective anode portions 126 as discussed above in reference to FIGS.3-4 .

Moreover, in the illustrated embodiment of FIGS. 8-9 , the inner cathode122 i has an at least substantially rectangular cross section (e.g.,having four at least substantially linear sides; having two at leastsubstantially linear sides and having two curved sides conforming to thecontour of the interior wall of the outer cathode 122 o), and theincluded cathode current collector 128 has a shape corresponding to theshape of the inner cathode 122 i. As shown in FIGS. 8-9 , for example,the cathode current collector has an at least substantially rectangularshape corresponding to the at least substantially rectangular shape ofthe inner cathode 122 i. Moreover, as shown specifically in theembodiment of FIG. 8 , for example, the cathode current collector 128may have sidewall lengths at least substantially half of the sidewalllengths of the inner cathode 122 i. In other embodiments, such as thatshown in FIG. 9 , the cathode current collector 128 may have sidewalllengths at least substantially similar to the sidewall lengths of theinner cathode 122 i, as the cathode current collector 128 may beembedded within the exterior surface of the inner cathode 122 i. Itshould be understood that the inner cathode 122 i may have any of avariety of alternative shapes (e.g., triangle, pentagon, hexagon, and/orthe like) and the cathode current collector 128 may have a shapecorresponding to the shape of the inner cathode 122 i.

FIG. 11 illustrates yet another example cell 210 having an “inside-out”design, with a single, annular cathode 222 positioned between a centralanode 226 i and an outer anode 226 o (having a separator 224 locatedbetween the cathode 222 and inner anode 226 i and between the cathode222 and the outer anode 226 o). In the illustrated embodiment of FIG. 11, the can side wall 212 functions as a current collector for the outeranode 226 o, and the closed bottom end 214 functions as a negativeterminal of the cell 210. Thus, Cell 210 of FIG. 11 includes an outer,ring-shaped anode 226 o disposed adjacent an interior surface of the canside wall 212 and surrounding the cathode 222 defined within a cavityformed by the outer anode 226 o. Moreover, the cathode 222 isring-shaped and surrounds the inner anode 226 i. Separator 224 isdisposed between the outer anode 226 o and the cathode 222 and isdisposed between the inner anode 226 i and the cathode 222. The outer,ring-shaped anode 226 o has a hollow, circular and cylindrical shapewith an internal surface that is generally smooth. The external surfaceof the outer anode 226 o conforms generally to the shape of the internalsurface of the can side wall 212. At least a portion of the externalsurface of the outer anode 226 o may be in direct contact with the canside wall 212, thereby utilizing the can side wall 212 as a currentcollector for the outer anode 226 o. By utilizing the can side wall 212as the current collector for the outer anode 226 o (the electrodelocated adjacent to the can side wall 212), the cell design may minimizeinactive materials in the form of a separate anode current collector,which would occupy volume within the cell 210 that could otherwise beoccupied by active materials. When the anode active material has a lowerelectrochemical redox potential in aqueous solution than the hydrogenredox potential, the hydrogen gassing rate from the inner surface of thecan side wall 212, which is in contact with the anode 226, can be veryhigh. Without appropriate accommodations, this high hydrogen gassingrate could lead to leakage of the aqueous electrolyte from the cell.Thus, the interior surface of the can side wall 212 may be plated with atin or an alloy of copper, tin, and/or zinc to substantially reduce thegassing rate at the anode/can interface. In such embodiments, a closedend 214 of the can may be embodied as a negative terminal of the cell210. Moreover, as shown in FIG. 11 , a central anode current collector229 (e.g., embodied as a nail) may be electrically connected with thecan (e.g., by welding the anode current collector 229 to the closedbottom end of the can) and may extend into the inner anode 226 i tooperate as a current collector for the central anode 226 i. It should beunderstood that other embodiments (not shown) may comprise a single,central cathode and a single anode (located around an exterior of thesingle cathode).

In other embodiments (not shown), an outer anode 226 o is electricallyinsulated from the can side wall 212 (e.g., by placement of a separatorlayer between the anode and the can side wall 212, by coating the canside wall with an insulating material, and/or the like), and is insteadin electrical contact with a current collector (not shown) electricallyconnected with a negative terminal of the cell 210. In variousembodiments, suitable materials for use as an anode current collectormay comprise copper and its alloys with zinc, and/or tin. Anode currentcollectors may be alloyed and/or coated with a metal having a highhydrogen overvoltage, such as zinc, indium, or tin, to reduce hydrogengas generation during storage and discharge of the cell. Thus, whenutilizing the cell can side wall 212 as the anode current collector, theinterior surface (or a portion thereof) may be coated with such amaterial to minimize hydrogen offgassing of the anode during storage anddischarge of the cell 110.

Cell 210 also has an annular seal 232 to seal the interior of thebattery and to electrically insulate the positive terminal cover 218from the negatively charged can 212. Moreover, as discussed in referenceto other inner cathode configurations discussed above, the cathode 222may have an associated cathode current collector 228 (e.g., a meshmaterial) embedded therein. The cathode current collector 228 may belocated within the interior of the cathode 222 and may have a shapecorresponding to the shape of the cathode 222. For example, in theembodiment of FIG. 11 , the cathode 222 may have a cylindrical shape,and the cathode current collector 228 may have a similar cylindricalshape. The cathode current collector 228 has a radius at leastsubstantially half of the radius of the cathode 222. However, it shouldbe understood that the cathode current collector 228 may have a size atleast substantially similar to the size of the cathode 222. For example,the cathode current collector 228 may be embedded within an exteriorsurface of the cathode 222.

Moreover, as shown in the embodiment of FIG. 11 the positive terminalcover 218 may be welded or otherwise electrically connected to thecathode current collector 228 via conducting member 241 (e.g., embodiedas a conductive tab, a conductive nail, or a combination thereof). Aninsulating jacket, such as the plastic film layer 220, and a negativeterminal cover (not shown), may also be included in embodiments of cell210. Moreover, as shown in FIG. 11 , the separator 224 of the cell maycomprise a closed bottom end 238 to electrically insulate the positivelycharged cathode 222 from the negatively charged can (specifically, fromthe negatively charged closed bottom end 214 of the can).

In certain embodiments, the cathode (e.g., outer cathode 122 o, innercathode 122 i, or cathode 222, depending on configuration) comprises amanganese oxide as a positive active material. The manganese oxide maybe any manganese oxide suitable as an active material in an alkalinezinc-manganese oxide cell. Manganese oxide suitable for use in variousembodiments may have a molecular formula close to MnO₂, and maytherefore be referred to as manganese dioxide. Examples of manganeseoxides that may be used are natural manganese dioxides (NMD), chemicalmanganese dioxides (CMD), and electrolytic manganese dioxides (EMD). EMDtypically has the greatest theoretical capacity because of itsrelatively high level of purity and high density.

In certain embodiments, the cathode (e.g., outer cathode 122 o, innercathode 122 i, or cathode 222, depending on configuration) may compriseanother positive active material besides a manganese oxide. Suitablealternative cathode active materials may be compatible with manganeseoxide used in the cell and may be selected and included to provide thecell with certain desired voltage and/or discharge characteristics.Examples of alternative active materials that may be used in combinationwith, and/or as an alternative to manganese oxide include, but are notlimited to, silver oxides, nickel oxides (e.g., Li_(x)Ni_(y)M_(z)O₂,wherein x<0.2, y≥0.6, z≤0.4), nickel oxyhydroxide and/or the like.

The cathode may contain other, non-active materials that providedesirable discharge characteristics of the cathode. For example, aconductive material, such as a carbon material (e.g., graphite,graphitized carbons, and/or the like), may be included within thecathode to improve the electrical conductivity of the cathode. Suitablegraphites include natural and synthetic graphites, unexpanded orexpanded graphites, and can be in a variety of forms, including powders,flakes, fibers, and/or the like.

Moreover, cathodes of certain embodiments additionally include one ormore binder materials. Suitable binder materials includepolytetrafluoroethylenes, polyethylenes, diblock copolymers of styrene,ethylene and propylene, polyacrylic acids, and poly (acrylicacid-co-sodium-4-styrene sulfonate). Binder materials may be used singlyor in combination, such as a blend (e.g., 3:1 by weight) ofpolytetrafluoroethylene and polyacrylic acid. It is generally desirableto keep the amount of binder to a minimum, but the amount used in anygiven electrode may vary, for example, based on the desired strength ofthe cathode for the manufacturing process used. As a non-limitingexample, a binder may be provided in the range from about 0.1 to 6.0weight percent of the weight of the cathode (e.g., between 0.2 wt % to2.0 wt %).

Additional additives may be included with the cathode of certainembodiments. Such additives may include, but are not limited to, bariumsulfate, titanium dioxide, n-type titanium dioxide, and/or the like.Such additives may be provided, for example, to improve dischargeperformance.

A small amount of water (e.g., 1.5 to 8.0 percent, based on the weightof the solid cathode materials), either with or without electrolyte saltdissolved therein, may be mixed with the dry cathode ingredients toachieve a desired consistency for cathode forming.

In certain embodiments, the volume percent solids in the cathode isgreater than or equal to 60 vol %. More preferably, a volume percentsolids of the cathode being greater than or equal to 70 vol % providesimproved low rate discharge performance. At least 75 vol % solidspacking is preferred, for example, between 76 vol % to 78 vol %.

The anode (e.g., anode 126 or anode 226) of an alkaline Zn/MnO₂ cell maycomprise a mixture of gelled zinc particles, an electrically conductivematerial, solid zinc oxide, and a surfactant. The anode may optionallyinclude other additives, for example, a binder or gelling agent, and/orthe like. The zinc may be in powder, mesh, wool, foam, 3D structure withwell-defined pore size/shape or flake form, or a combination thereof. Anamalgamated zinc alloy comprising bismuth, indium, and aluminum may beadvantageous. Zinc powder, for example, having a ids( )of about 110 μmmay be utilized. The anode may additionally comprise water, electrolyte(e.g., potassium hydroxide), and a gelling agent (e.g., acrylic acid).Other additives may be included in the anode 126 as well, such asgassing inhibitors (e.g., In(OH)₃, ZnO, and sodium silicate), and/orother additives providing desirable anode characteristics may beprovided. In an embodiment, the anode comprises a gelled electrolyte,wherein the gelled electrolyte is prepared by combining a gelling agentwith a first aqueous alkaline electrolyte solution, wherein the firstaqueous alkaline electrolyte solution comprises an alkaline metalhydroxide electrolyte and dissolved zinc oxide. In a further embodiment,the first aqueous alkaline electrolyte solution comprises dissolved zincoxide in an amount of ≥2.5, ≥2.6, ≥2.7, ≥2.8, ≥2.9, ≥3.0, ≥3.1, ≥3.2,≥3.3, ≥3.4, ≥3.5, ≥3.6, ≥3.7, ≥3.8, ≥3.9, or ≥4.0 weight percent. In anembodiment, the first aqueous alkaline electrolyte solution comprisesdissolved zinc oxide in an amount of about 2.7-3.3 weight percent.

The anode may have a solids content of at least 27 vol % solids. In someembodiments, the anode may have a 31.5 vol % or higher solids percent.Zinc concentrations of 66 wt % or higher, for example between 70 to 76wt % provide excellent discharge characteristics on low rate and highrate discharge. The anode may be sufficiently gelatinous so as to flowand conform to the shape of a container. As discussed herein, the gelledanode may, in certain embodiments, be poured/extruded/provided into aninterior opening of an outer cathode ring (separated by a separatorlayer), and then an inner cathode (having a separator layer coatedtherein) may be inserted into the center of the gelled anode, therebydisplacing the anode into the anode ring between the inner cathodeportion and the outer cathode portion.

In certain embodiments, a cell according to various embodiments may havean anode to cathode (A:C) ratio between about 1-1.3 (including both theinner cathode and the outer cathode, if applicable, within thecalculation). As just one example, an LR6 battery having an outercathode and an inner cathode (e.g., having a configuration according toone of FIGS. 3-4 , may have an outer cathode thickness of about 0.011 to0.094 inches, preferably about 0.029 to 0.081 inches, and morepreferably about 0.048 to 0.075 inches, and an inner cathode diameter ofabout 0.406 to 0.136 inches, preferably about 0.358 to 0.192 inches, andmore preferably about 0.303 to 0.215 inches. The anode ring, positionedbetween the outer cathode and the inner cathode, may have a thickness ofabout 0.054 to 0.105 inches, preferably about 0.059 to 0.090 inches, andmore preferably about 0.068 to 0.084 inches.

The electrolyte may comprise KOH. The total KOH concentration in theelectrolyte in a completed, undischarged cell may be from about 25 toabout 50 wt %, generally from about 36 to about 40 wt %.

A surfactant that is either a nonionic or anionic surfactant, or acombination thereof is present in the anode. It has been found thatanode resistance is increased during discharge by the addition of solidzinc oxide alone, but is mitigated by the addition of the surfactant.The addition of the surfactant increases the surface charge density ofthe solid zinc oxide and lowers anode resistance as indicated above. Useof a surfactant is believed to aid in forming a more porous dischargeproduct when the surfactant adsorbs on the solid zinc oxide. When thesurfactant is anionic, it carries a negative charge and, in alkalinesolution, surfactant adsorbed on the surface of the solid zinc oxide isbelieved to change the surface charge density of the solid zinc oxideparticle surfaces. The adsorbed surfactant is believed to cause arepulsive electrostatic interaction between the solid zinc oxideparticles. It is believed that the surfactant reduces anode resistanceincrease caused by the addition of solid zinc oxide because the adsorbedsurfactant on solid zinc oxide results in enhanced surface chargedensity of solid zinc oxide particle surface. The higher the BET surfacearea of solid zinc oxide, the more surfactant can be adsorbed on thesolid zinc oxide surface.

The anode comprises solid zinc oxide in an amount from about 0.5 to 5weight percent, based on the total weight of the anode. In a preferredembodiment, the anode comprises solid zinc oxide in an amount from about1 to 4 weight percent. In an embodiment, the solid zinc oxide issubstituted, so as to reduce its solubility.

Other components which may be optionally present within the anodeinclude, but are not limited to, gassing inhibitors, organic orinorganic anticorrosive agents, plating agents, binders or othersurfactants. Examples of gassing inhibitors or anticorrosive agents caninclude indium salts, such as indium hydroxide, perfluoroalkyl ammoniumsalts, alkali metal sulfides, etc. In a further embodiment, sodiumsilicate in an amount of about 0.3 weight percent based on the totalweight of the anode electrolyte is preferred in the anode in order tosubstantially prevent cell shorting through the separator (e.g.,separator 124 or separator 224) during cell discharge.

Method of Manufacture

A central cathode (e.g., inner cathode 122 i and/or cathode 222) inaccordance with various embodiments may be formed via one or moremanufacturing methods. The central cathode may be formed outside of thecell can, or may be formed in place within the cell can.

Before forming the cathode, the cathode current collector may be formed,by wrapping a current collector material (e.g., a current collectormesh, a perforated foil, a wire, and/or the like) around a die having across-sectional shape corresponding to the desired shape of the currentcollector. For example, to form a cylindrical cathode current collector,the mesh current collector material may be wrapped around a cylindricaldie. In certain embodiments, the current collector material may bewrapped until opposing edges meet. In other embodiments, the currentcollector material may be wrapped until opposing edges overlap at leastpartially. The opposing edges may be secured relative to one another(e.g., via spot welding) to maintain the desired cross-sectional shapeof the current collector. In various embodiments, such as those forminga current collector for placement within an embodiment configured inaccordance with FIG. 3 or FIG. 4 discussed herein, a conducting member,such as a conducting tab 141 or a conducting plate 142 is securedrelative to the current collector (e.g., by welding).

As just one example, the central cathode may be molded outside of thecell can. The central cathode may be formed as a single, continuouspiece, by filling a mold with a cathode mixture (as discussed above),and subjecting the cathode mixture within the mold to a high pressure toform the cathode cylinder. In certain embodiments, the cathode currentcollector 128, 228 may be positioned within the central cathode moldprior to filling the mold with the cathode mixture, and the cathodemixture may then be added to the central cathode mold around the currentcollector, such that it falls within the openings of the currentcollector. For example, a plug may be added to an end of the centralcurrent collector, such that the cathode material first fills the regionbetween the walls of the mold and the exterior surface of the currentcollector. Thereafter, the plug may be removed, and cathode material maybe added to the interior of the current collector. The combination ofthe cathode material and the current collector mesh may then be subjectto a high pressure to form the cylindrical cathode with embedded cathodecurrent collector. As discussed herein, the cathode current collector128, 228 may comprise a cylindrical mesh material (e.g., having oppositeopen ends) with a conductive tab 141 extending from one longitudinalend, that may be positioned at least substantially coaxially with thecentral cathode (and accordingly with the cathode mold, duringmanufacturing) at a medial radial location (e.g., midway between thecentral axis of the cathode/cathode mold and the outer surface of thecathode/cathode mold. As noted, the conducting tab 141 may be connected(e.g., via welding) before forming the cathode with integrated currentcollector, or after forming the cathode with the integrated currentcollector. In other embodiments comprising a conducting plate 142, theconducting plate 142 may be attached (e.g., via welding) relative to thecathode current collector prior to forming the cathode with integratedcurrent collector. In other embodiments, the conducting plate 142 may beattached (e.g., via welding) relative to the cathode current collectorafter forming the cathode with integrated current collector.

It should be understood that press-molding the cathode with theintegrated cathode current collector may not result in a substantialchange in length of the cathode current collector, and therefore thecathode current collector mesh does not apply a substantial expanding,tensile force to the resulting cylindrical cathode. In otherembodiments, the cathode current collector may be compressed duringformation of the cathode with integrated cathode current collector.However, the cathode current collector may be characterized by a lowspring force, and accordingly the cathode current collector may notapply a substantial expanding, tensile force to the resultingcylindrical cathode 122.

As another example, the central cathode may be formed as a single,continuous piece, by filling a mold with a cathode mixture (as discussedabove), and subjecting the cathode mixture within the mold to a highpressure to form the cathode cylinder. The central cathode may be formedwithout the cathode current collector embedded therein. After removingthe central cathode from the forming mold, the current collector (e.g.,current collector mesh) may be rolled around the exterior of the cathodecylinder to form the cathode current collector. The cathode currentcollector may have a diameter slightly smaller than the diameter of theresulting central cathode, such that the cathode current collector ispressed into the surface of the central cathode, such that the cathodecurrent collector is positioned within the diameter of the centralcathode.

As yet another example, the central cathode may be formed as acombination of a plurality of cathode pellets, each cathode pellet beinga cylindrical cathode pellet having a diameter equal to the diameter ofthe resulting cathode. Each cathode pellet may be molded, by filling amold with cathode material and pressing the cathode material to form thecathode pellet. As one non-limiting example, a cathode pellet for a LR6cell may be formed within a die having a diameter of 0.189 inches. 0.755g of cathode mix is added to the die and pressed at 2600 lb of force toform a cathode pellet having a length of 0.494 inches and a diameter of0.189 inches. A plurality of cathode pellets may be stacked end-to-end(e.g., 4 cathode pellets) to form the length of the cathode. The currentcollector mesh may be rolled around the exterior of the stack of theplurality of cathode pellets to form the cylindrical current collector.The cylindrical current collector may have a diameter slightly smallerthan the diameter of the resulting central cathode, such that thecylindrical current collector mesh is pressed into the surface of thecentral cathode, such that the cylindrical current collector ispositioned within the diameter of the central current collector. In suchembodiments, the current collector mesh structurally connects theplurality of cathode pellets, to provide a single cathode structure withsufficient strength and resilience to withstand handling during the cellmanufacturing process (e.g., specifically, to withstand placement of aseparator around an exterior surface of the cathode and/or placement ofthe cathode (with or without wrapped separator) into the cell can).

As yet another example manufacturing technique, the central cathode maybe extruded, for example with or without an included cathode currentcollector. As just one specific example, an at least substantiallycontinuous cathode current collector tube (e.g., comprising a cathodecurrent collector mesh) may be fed through a generally cylindricalextrusion die, while simultaneously the cathode material is extrudedthrough the same extrusion die. The cathode current collector tube ispositioned as desired within the extrusion die to generate a cathodestructure with an embedded cathode current collector in a desiredposition. As noted above, the cathode current collector may bepositioned at a mid-point on the radius of the cathode, and accordinglythe cathode current collector may be positioned substantially at amid-point on the radius of the extrusion die. As cathode material issimultaneously extruded through the extrusion die, the cathode materialfills the apertures of the mesh to create an at least substantiallycontinuous cathode structure having a desired solids packing percentage.It should be understood that the cathode current collector may have afeed rate through the extrusion die at least substantially equal to thefeed rate of the cathode material through the feed die, thereby avoidingundesirable tensile or compressive forces internal to the cathodestructure that may decrease the strength and/or resilience of thecathode structure to remaining steps of the cell manufacturing process.

As the cathode structure is extruded, individual cathodes may be cutfrom the continuous cathode cylinder extending from the extrusion die.

As mentioned above, the cathode material may be extruded without anembedded cathode current collector. In such embodiments, the cathodematerial may be fed through the extrusion die to create a cylindricalcathode. The cathode structure may be cut to length to form cathodes forpositioning within cell cans. After extrusion (and either before orafter cutting the cathodes to length) the current collector mesh may berolled around the exterior of the cathode to form the cathode currentcollector. The cathode current collector may have a diameter slightlysmaller than the diameter of the resulting central cathode, such thatthe cathode current collector mesh is pressed into the surface of thecentral cathode, such that the cathode current collector is positionedwithin the diameter of the central cathode.

As alluded to above, the separator may be wrapped around an exteriorsurface of the cathode prior to placement of the same within the cellcan. In certain embodiments, the separator may overlap one or both endsof the cathode structure, thereby providing insulting properties to oneor both ends of the cathode structure to prevent undesirable shortcircuits between the cathode and the anode (or anode current collector)within the completed cell. However, it should be understood that theseparator may be placed within the cell can prior to placement of thecathode structure within the cell can, as may be desired according tocertain manufacturing techniques.

The separator comprises an ionically conductive, electrically insulatingmaterial to separate the anode and cathode within the cell. Theseparator maintains a physical dielectric separation of the cathode'selectrochemically active material from the electrochemically activematerial of the anode and allows for transport of ions between theelectrode materials. In addition, the separator acts as a wicking mediumfor the electrolyte and as a collar that prevents fragmented portions ofthe negative electrode from contacting the top of the positiveelectrode. Separator can be a layered ion permeable, non-woven fibrousfabric. A typical separator usually includes two or more layers ofpaper. The separator may be formed either by pre-forming the separatormaterial into a cup-shaped basket having a closed bottom portion that issubsequently inserted into a cavity defined by anode and the closed endof the can (if the anode is inserted prior to the central cathode), orforming a basket during cell assembly by inserting two rectangularsheets of separator into the cavity with the material angularly rotated90° relative to each other. Conventional pre-formed separators aretypically made up of a sheet of non-woven fabric rolled into acylindrical shape that conforms to the inside walls of the anode and hasa closed bottom end.

The anode can be formed in a number of different ways as known in theart. For example, the anode components can be dry blended and added tothe cell, with alkaline electrolyte being added separately or apre-gelled anode process is utilized.

In one embodiment, the zinc and solid zinc oxide powders, and otheroptional powders other than the gelling agent, are combined and mixed.Afterwards, the surfactant is introduced into the mixture containing thezinc and solid zinc oxide. A pre-gel comprising alkaline electrolytesolution, soluble zinc oxide and gelling agent, and optionally otherliquid components, are introduced to the surfactant, zinc and solid zincoxide mixture which are further mixed to obtain a substantiallyhomogenous mixture before addition to the cell. Alternatively, in afurther preferred embodiment, the solid zinc oxide is predispersed in ananode pre-gel comprising the alkaline electrolyte, gelling agent,soluble zinc oxide and other desired liquids, and blended, such as forabout 15 minutes. The solid zinc oxide and surfactant are then added andthe anode is blended for an additional period of time, such as about 20minutes. The amount of gelled electrolyte utilized in the anode isgenerally from about 25 to about 35 weight percent, and for example,about 32 weight percent based on the total weight of the anode. Volumepercent of the gelled electrolyte may be about 70% based on the totalvolume of the anode 126.

The anode may be inserted into the cell in any suitable manner. If ananode is flowable when it is added to the cell, it may be disposed as aliquid to flow to fill the space between the central cathode (andseparator) and the can side wall (or the interior surface of an outercathode 122 o (and separator) as discussed herein). Thus, the anode maybe added into the can after placement of the outer cathode 122 o andseparator within the interior of the cell can. The inner cathode 122 i(and associated separator) may be added to the interior of the cellafter adding the flowable anode material thereto. As the inner cathode122 i is added to the cell, the anode material is displaced into theregion between the inner cathode 122 i and outer cathode 122 o. Becausethe inner cathode 122 i is added together with the correspondingseparator, the anode material does not contact the cathode materialduring insertion of the inner cathode.

In other embodiments, the flowable anode material may be dispersed intothe cell after placement of the both outer cathode 122 o and innercathode 122 i. For example, in embodiments including a bottom conductorplate 142 secured relative to the inner cathode 122 i, the inner cathode122 i may be placed within the cell prior to placement of the anodematerial therein. Moreover, after placement of the inner cathode 122 iand outer cathode 122 o within the cell, a bottom cup 125 (e.g.,comprising a separator material and/or another insulator material) maybe placed within the cell, between the outer cathode 122 o and innercathode 122 i prior to placement of the anode material therein, so as tomaintain electrical insulation between the anode material and thecathode's conducting plate 142.

In other embodiments, the anode may be dispensed into the cell underpressure, for example, by extrusion. If an anode is a solid, such as apacked mass of particulate anode material or a continuous 3 dimensional(3D) anode (e.g., comprising an active material of zinc and/or one ormore additives), the anode may be formed into a desired shape prior toinsertion of the same into the cell. In such embodiments, the anode maybe added to the cell can after the outer cathode 122 o and/or the innercathode 122 i (or central cathode 222), as mentioned above. Inembodiments including an inner cathode 122 i and outer cathode 122 o,the anode 126 may be positioned within the cell after placement of theouter cathode 122 o (which may be formed in place via impact moldingand/or which may be formed outside of the cell, for example, via ringmolding, and added to the cell can) but before placement of the innercathode 122 i.

Moreover, the anode may be formed into a desired shape outside of thecell (e.g., by ring molding the anode into one or more anode rings thatmay be added to fill the cell can with a desired anode quantity). Insuch embodiments, a plurality of anode rings (e.g., 3 or 4 anode rings)may be individually placed into the cell can to provide a desiredquantity of anode therein. In other embodiments, a single anode tube (acylindrical anode having an open center) may provide the entire quantityof anode material desired for a particular cell 110. Thereafter, theseparator and cathode material may be added to the central opening ofthe anode (in one or more steps).

In other embodiments, the anode may be formed into a desired ring shapewithin the cell can. For example, impact molding may be utilized, bypouring particulate anode active material into the cell can, andinserting a ram into the center of the cell can to impact mold the anodematerial into a ring pressed against an interior surface of the cellcan. Thereafter, the separator and cathode material may be added to thecentral opening of the anode (in one or more steps).

In addition to the aqueous alkaline electrolyte absorbed by the gellingagent during the anode manufacturing process, an additional quantity ofan aqueous solution of alkaline metal hydroxide, i.e., “freeelectrolyte,” may added to the cell during the manufacturing process.The free electrolyte may be incorporated into the cell by disposing itinto the cavity defined by the cathode or anode, or combinationsthereof. The method used to incorporate free electrolyte into the cell110 is not critical provided it is in contact with the anode, cathode,and separator. In one embodiment, free electrolyte is added both priorto addition of the anode mixture as well as after addition. In oneembodiment, about 0.97 grams of 34 weight percent KOH solution is addedto an LR6 type cell as free electrolyte. This free electrolyte solutioncomprises dissolved zinc oxide in a range of about 0.01-6.0 weightpercent. In embodiments, the free electrolyte solution comprisesdissolved zinc oxide in an amount of greater than, less than, or equalto about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2,1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6,2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0,4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4,5.5, 5.6, 5.7, 5.8, 5.9, 6.0 weight percent, or in any range between twoof these values. In a preferred embodiment, the free electrolytesolution comprises dissolved zinc oxide in an amount of between about4.0-6.0 weight percent. The free electrolyte solution may be about 85%,86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, or100% saturated with dissolved zinc oxide.

In an embodiment, the free electrolyte solution comprises potassiumhydroxide (KOH), sodium hydroxide (NaOH), lithium hydroxide (LiOH),magnesium hydroxide (Mg(OH)₂), calcium hydroxide (Ca(OH)₂), magnesiumperchlorate (Mg(ClO₄)₂), magnesium chloride (MgCl₂), or magnesiumbromide (MgBr₂).

As an example, a shot of free electrolyte may be added to the cell afterinsertion of the anode and/or cathode into the cell. In one example, oneor more shots of free electrolyte may be added to the cell afterinsertion of the anode, cathode, and separator into the cell interior.Once the active materials are added to the cell, the cell may be sealedwith annular seal and one or more covers, and the cell can may becrimped to close the open end of the cell can to form the complete cell.In certain embodiments, a plastic film label (e.g., a heat-shrink label)may be secured to the exterior of the cell and formed over theperipheral edges of the can, to provide insulation against incidentalshort-circuit connection between the positive and negative terminals ofthe battery cell.

The foregoing descriptions of assembly methods should be taken as mereexamples. The sequence of inserting the electrodes, separator, andelectrolyte into the cell may be varied to best suit the compositionsand shapes of those components.

While embodiments have been illustrated and described in detail above,such illustration and description are to be considered illustrative orexemplary and not restrictive. It will be understood that changes andmodifications may be made by those of ordinary skill within the scopeand spirit of the following claims. In particular, embodiments includeany combination of features from different embodiments described aboveand below.

The embodiments are additionally described by way of the followingillustrative non-limiting examples that provide a better understandingof the embodiments and of its many advantages. The following examplesare included to demonstrate preferred embodiments. It should beappreciated by those of skill in the art that the techniques disclosedin the examples which follow represent techniques used in theembodiments to function well in the practice of the embodiments, andthus can be considered to constitute preferred modes for its practice.However, those of skill in the art should, in light of the presentdisclosure, appreciate that many changes can be made in the specificembodiments which are disclosed and still obtain a like or similarresult without departing from the spirit and scope of the embodiments.

EXAMPLES

The discharge performance of batteries provided in accordance withembodiments discussed herein were tested against traditionalbobbin-style cells, having a centrally located anode. The results ofcell real impedance measurements and Digital Still Camera (DSC) test ofhigh discharge performance of the batteries are shown in TABLE 1, below,and select discharge data on the DSC test is illustrated in the chart ofFIG. 10 . The DSC test is a high power test, having testing protocolsconsisting of discharging a cell at alternating loads of 1500 mW for 2seconds and 650 mW for 28 seconds for 5 minutes each hour, until thecell is determined to have a remaining potential of 1.05V representingthe cell's functional end point (FEP). Cell impedance is the real partof the complex impedance of the cell measured under a 10 mV voltageamplitude at 10 kHz using a four-wire connection. The instrument usedfor the cell impedance measurement was a Solarton Potentiostat (model1287) coupled with a Solartron Frequency Analyzer (model 1250).

TABLE 1 Cell real Ref. impedance DSC service # Cell construction (Ohms)(minutes) 1 Bobbin construction, 0.041 54 FIG. 1-2 (comparison) 2 Dualcathode (comparison) 0.038 96 3 Split anode A/C = 1.13 0.032 104(comparison). 4 Split anode A/C = 1.26 0.025 94 (comparison). 5 Dualcathode, FIG. 3 lot A 0.024 139 6 Dual cathode, FIG. 3 lot B 0.027 124 7Dual cathode, FIG. 6 0.022 125 8 Split anode, FIG. 8 0.024 120 A/C =1.13 9 Split anode, FIG. 8 0.025 114 A/C = 1.26

Rows 1-4 of TABLE 1 provide data indicative of comparative test resultsfrom tests of reference cells, illustrating the tested cell impedanceand DSC service for comparative reference cell designs. The data of Row1 is additionally reflected at line 10 of FIG. 10 .

Rows 5-9 of TABLE 1 provide data indicative of the cell real impedanceand DSC service for cells having configurations according to variousembodiments.

TABLE 2 provides a description of the construction of each of the testedcells. The descriptions of the cells provided in corresponding columnsof TABLE 2 may be cross-referenced with the results for thecorresponding cells provided in rows of TABLE 1 by the included Ref #(indicated in the first column of TABLE 1 and the first row of TABLE 2).

TABLE 2 Ref. # 1 2 3 4 5 6 7 8 9 Description Bobbin Dual Split SplitDual Dual Dual Split Split construction cathode anode anode cathodecathode cathode anode anode A/C = A/C = lot A lot B A/C = A/C = 1.131.26 1.13 1.26 Cathode 11.52 11.77 11.45 10.99 11.07 11.07 11.07 11.4510.99 weight (g) Cathode formulation EMD, wt % 91.62 91.62 91.33 91.3391.33 91.33 91.33 91.33 91.33 Expanded 3.66 3.66 3.95 3.95 3.95 3.953.95 3.95 3.95 graphite (GA17 from Superior Graphite), wt % 40 wt % 3.033.03 3.04 3.04 3.04 3.04 3.04 3.04 3.04 KOH solution, wt % Coathylene0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 binder, wt % Additives,1.59 1.59 1.59 1.59 1.59 1.59 1.59 1.59 1.59 wt % Anode 6.29 6.25 5.816.20 6.25 6.25 6.25 5.81 6.20 weight (g) Anode formulation Zinc alloy69.87 69.87 69.87 69.87 69.87 69.87 69.87 69.87 69.87 powder (Bi, In andAl alloying elements), wt % 28 wt % 29.13 29.13 29.13 29.13 29.13 29.1329.13 29.13 29.13 KOH solution, wt % ZnO, wt % 0.29 0.29 0.29 0.29 0.290.29 0.29 0.29 0.29 Gelling 0.45 0.45 0.45 0.45 0.45 0.45 0.45 0.45 0.45agent, wt % Additives, 0.26 0.26 0.26 0.26 0.26 0.26 0.26 0.26 0.26 wt %

A first reference cell, corresponding to the data of row 1 of TABLE 1,column 1 of TABLE 2, and line 10 of FIG. 10 , has a construction asillustrated in FIGS. 1-2 . The outer cathode ring of the reference cellhas a composition of _91.62 wt % EMD, 3.66 wt % expanded graphite, 3.03wt % of KOH solution (concentration of the KOH is 40 wt %), and 0.10 wt% coathylene binder, and 1.59 wt % additives, and is formed by ringmolding to form the outer cathode structure of the cell. A gelled anodehaving a composition of 69.87 wt % zinc alloy powder containing Bi, In,and Al, 29.13 wt % KOH solution (having a concentration of 28 wt %),0.29 wt % ZnO, 0.45 wt % gelling agent, and 0.26 wt % additives ispositioned within the central cavity of the cathode structure, and a twolayers of separator material each having a 0.003″ thickness ispositioned between the cathode and the anode. As shown in FIG. 1 , acentral current collector pin is utilized in association with the anode,and the cell can itself is utilized as a current collector for thecathode. With reference to FIG. 10 , the reference cell was determinedto have a runtime of 54 minutes under testing conditions of the DSC test(the runtime being defined as the amount of time for the battery todischarge from a new, undischarged state until the voltage output of thebattery decreases to less than 1.050 V) and a cell impedance of 0.041ohms.

A second reference cell, corresponding to the data of row 2 of TABLE 1,column 2 of TABLE 2, and line 11 of FIG. 10 was also included within thetest results. The second reference cell has a dual-cathode construction,characterized by an outer cathode and an inner cathode and an annularanode ring positioned between the outer cathode and the inner cathode,and the inner cathode is defined within a central cavity of the anode.The anode ring of the second reference cell has a composition of 69.87wt % zinc alloy powder containing Bi, In, and Al, 29.13 wt % KOHsolution (the concentration of KOH is 28 wt %), 0.29 wt % ZnO, 0.45 wt %gelling agent, and 0.26 wt % additives, and is formed by dispensing theflowable anode gel into the anode cavity. The outer cathode and theinner cathode comprise similar cathode compositions. The cathode has acomposition of 91.62 wt % EMD, 3.66 wt % expanded graphite, 3.03 wt % ofKOH solution (concentration of the KOH is 40 wt %), and 0.10 wt %coathylene binder, and 1.59 wt % additives, and the inner cathodeincludes an embedded mesh sheet current collector therein. The meshsheet current collector is defined by a flat mesh sheet folded into anaccordion configuration, and disposed within the central cathode toextend along the length of the center cathode. As shown at line 11 ofFIG. 10 , the second reference cell was determined to have a runtime of96 minutes under the testing conditions of the DSC test and an impedanceof 0.038 ohms.

A third reference cell, corresponding to the data of row 3 of TABLE 1and column 3 of TABLE 2 was also included within the test results. Thethird reference cell has split anode construction, having an outercathode surrounding two “D”-shaped anodes, each having a correspondingnail-shaped current collector therein. The two D-shaped anodes arepositioned on opposite sides of an at least substantially rectangularinner cathode including an embedded mesh sheet current collectortherein. The third reference cell has an A/C ratio of 1.13. The meshsheet current collector is defined by a flat mesh sheet folded into anaccordion configuration, and disposed within the central cathode toextend along the length of the center cathode. As shown in TABLE 1,above, the third reference cell was determined to have a runtime of 104minutes under the testing conditions of the DSC test and an impedance of0.032 ohms.

A fourth reference cell, corresponding to the data of row 4 of TABLE 1and column 4 of TABLE 2 was also included within the test results. Thefourth reference cell has a split anode construction analogous to thatdiscussed in reference to the third reference cell, having an outercathode surrounding two “D”-shaped anodes, each having a correspondingnail-shaped current collector therein. The two D-shaped anodes arepositioned on opposite sides of an at least substantially rectangularinner cathode including an embedded mesh sheet current collectortherein. The third reference cell has an A/C ratio of 1.26. The meshsheet current collector is defined by a flat mesh sheet folded into anaccordion configuration, and disposed within the central cathode toextend along the length of the center cathode. As shown in TABLE 1,above, the third reference cell was determined to have a runtime of 104minutes under the testing conditions of the DSC test and an impedance of0.025 ohms.

Finally, experimental cells having configurations in accordance withvarious embodiments discussed herein were tested. A first experimentalcell (data for which is reflected in Row 5 of TABLE 1, Column 5 of TABLE2, and line 12 of FIG. 10 ) and second experimental cell (data for whichis reflected in Row 6 of TABLE 1 and column 6 of TABLE 2) each have adual-cathode configuration as illustrated in FIG. 3 , including an outercathode and an inner cathode, and an annular anode positionedtherebetween. The anode ring of the first experimental cell and secondexperimental cell each have a composition of 69.87 wt % zinc alloypowder containing Bi, In, and Al, 29.13 wt % KOH solution (theconcentration of KOH is 28 wt %), 0.29 wt % ZnO, 0.45 wt % gellingagent, and 0.26 wt % additives, and is formed by dispensing the flowableanode gel into the anode cavity. The outer cathode and the inner cathodecomprise similar cathode compositions. The cathode has a composition of91.33 wt % EMD, 3.95 wt % expanded graphite, 3.04 wt % of KOH solution(concentration of the KOH is 40 wt %), and 0.1 wt % coathylene binder,and 1.59 wt % additives, and includes a cylindrical mesh currentcollector that is at least substantially concentric with the cathode.Within the LR6 experimental cell, the cylindrical mesh current collectorhas a diameter of at least approximately 2 mm, formed by wrapping a flatmesh sheet around a 2-mm diameter, round forming die. Thus, thecylindrical mesh current collector is located at least approximately atthe mid-point of the radius of the central cathode. As shown at line 12of FIG. 10 , the first experimental cell was determined to have aruntime of 139 minutes under the testing conditions of the DSC test (andan impedance of 0.024 ohms) approximately a 257% increase in runtime ascompared with the first reference battery. The second experimental cellwas determined to have a runtime of 124 minutes under DSC testingconditions and an impedance of 0.027 ohms, as reflected at row 6 ofTABLE 1.

A third experimental cell, having a configuration as shown in FIGS. 6-7was also tested. The third experimental cell has a dual-cathodeconfiguration, including an outer cathode and an inner cathode, and anannular anode positioned therebetween. The anode ring of the firstexperimental cell and second experimental cell each have a compositionof 69.87 wt % zinc alloy powder containing Bi, In, and Al, 29.13 wt %KOH solution (the concentration of KOH is 28 wt %), 0.29 wt % ZnO, 0.45wt % gelling agent, and 0.26 wt % additives, and is formed by dispensingthe flowable anode gel into the anode cavity. The outer cathode and theinner cathode comprise similar cathode compositions. The cathode has acomposition of 91.33 wt % EMD, 3.95 wt % expanded graphite, 3.04 wt % ofKOH solution (concentration of the KOH is 40 wt %), and 0.1 wt %coathylene binder, and 1.59 wt % additives. The inner cathode comprises4 stacked cathode pellets, which are collectively wrapped with acylindrical mesh current collector embedded within the exterior surfaceof the stacked cathode pellets. As shown in TABLE 1, the thirdexperimental cell was determined to have a runtime of 125 minutes underthe testing conditions of the DSC test and an impedance of 0.022, asreflected at row 7 of TABLE 1 (the construction of this experimentalcell is reflected at column 7 of TABLE 2).

A fourth experimental cell, having a configuration as shown in FIG. 8and having a construction reflected at column 8 of TABLE 2 was tested.The fourth experimental cell has a split anode construction, having anouter cathode surrounding two “D”-shaped anodes, each having acorresponding nail-shaped current collector therein. The two D-shapedanodes are positioned on opposite sides of an at least substantiallyrectangular inner cathode including an embedded mesh current collectortherein. The fourth experimental cell had an A/C ratio of 1.13. As shownin FIG. 8 , the mesh current collector has a rectangular cross-sectionhaving a shape corresponding with the shape of the inner cathode. Themesh current collector has side-wall lengths shorter than the sidewalllengths of the inner cathode, such that the mesh current collector isformed within the interior of the inner cathode. As shown in row 8 ofTABLE 1, above, the fourth experimental cell was determined to have aruntime of 120 minutes under the testing conditions of the DSC test andan impedance of 0.024 ohms.

Finally, a fifth experimental cell, having a configuration as shown inFIG. 8 and as discussed in reference to the fourth experimental cell wastested. The fifth experimental cell had an A/C ratio of 1.26 and aconstruction as reflected in column 9 of TABLE 2. As shown in row 9 ofTABLE 1, above, the fourth experimental cell was determined to have aruntime of 114 minutes under the testing conditions of the DSC test andan impedance of 0.025 ohms.

CONCLUSION

Many modifications and other embodiments will come to mind to oneskilled in the art to which this disclosure pertains having the benefitof the teachings presented in the foregoing descriptions and theassociated drawings. Therefore, it is to be understood that thedisclosure is not to be limited to the specific embodiments disclosedand that modifications and other embodiments are intended to be includedwithin the scope of the appended claims. Although specific terms areemployed herein, they are used in a generic and descriptive sense onlyand not for purposes of limitation.

That which is claimed:
 1. A method of manufacturing an electrochemicalcell, the method comprising: placing an outer cathode ring within acontainer, wherein the outer cathode ring is in contact with an interiorsurface of the container and defines a cathode opening bounded by aninner surface of the outer cathode ring; covering the inner surface ofthe outer cathode ring with a separator material; disposing an anodematerial within the cathode opening, wherein the anode material isseparated from the container and the outer cathode ring by theseparator; positioning an inner cathode comprising an embedded cathodecurrent collector and covered with a separator within the cathodeopening of the outer cathode ring, thereby displacing at least a portionof the anode material into a gap defined between the inner surface ofthe outer cathode ring and an outer surface of the inner cathode;electrically connecting the cathode current collector with thecontainer; extending an anode current collector into the anode material;and sealing the container with a cover, wherein the cover is inelectrical connection with the anode current collector.
 2. The method ofclaim 1, wherein electrically connecting the cathode current collectorwith the container comprises attaching a conducting tab between thecathode current collector and the container.
 3. The method of claim 1,further comprising electrically insulating the conducting tab from theanode and anode current collector.
 4. The method of claim 1, whereinpositioning an inner cathode within the cathode opening furthercomprises: forming a plurality of cathode pellets; stacking theplurality of cathode pellets axially; embedding the cathode currentcollector within an exterior surface of the plurality of cathode pelletsto form the inner cathode; and wrapping the inner cathode with theseparator material.
 5. The method of claim 1, wherein the cathodecurrent collector has a shape corresponding to a shape of the innercathode.
 6. The method of claim 5, wherein the inner cathode and thecathode current collector are at least substantially cylindrical and thecathode current collector is at least substantially concentric with theinner cathode, and wherein the cathode current collector has a diameterat least substantially half of a diameter of the inner cathode.
 7. Themethod of claim 5, wherein the inner cathode and the cathode currentcollector are at least substantially rectangular.
 8. The method of claim1, wherein the cathode current collector is a conductive tube.
 9. Themethod of claim 8, wherein the conductive tube comprises a conductivemesh.
 10. The method of claim 9, wherein the conductive tube comprises aperforated material.
 11. A method of manufacturing an electrochemicalcell, the method comprising: placing an outer cathode ring within acontainer, wherein the outer cathode ring is in contact with an interiorsurface of the container and defines a cathode opening bounded by aninner surface of the outer cathode ring; covering the inner surface ofthe outer cathode ring with a separator material; positioning an innercathode comprising an embedded cathode current collector and coveredwith a separator within the cathode opening of the outer cathode ringsuch that an outer surface of the inner cathode is spaced apart from theinner surface of the outer cathode ring; disposing an anode materialbetween the outer cathode and the inner cathode; electrically connectingthe cathode current collector with the container; extending an anodecurrent collector into the anode material; and sealing the containerwith a cover, wherein the cover is in electrical connection with theanode current collector.
 12. The method of claim 11, whereinelectrically connecting the cathode current collector with the containercomprises attaching a conducting plate between the cathode currentcollector and a closed bottom end of the container.
 13. The method ofclaim 12, further comprising electrically insulating the conductingplate from the anode.
 14. The method of claim 11, wherein positioning aninner cathode within the cathode opening further comprises: forming aplurality of cathode pellets; stacking the plurality of cathode pelletsaxially; embedding the cathode current collector within an exteriorsurface of the plurality of cathode pellets to form the inner cathode;and wrapping the inner cathode with the separator material.
 15. Themethod of claim 11, wherein the cathode current collector has a shapecorresponding to a shape of the inner cathode.
 16. The method of claim15, wherein the inner cathode and the cathode current collector are atleast substantially cylindrical and the cathode current collector is atleast substantially concentric with the inner cathode, and wherein thecathode current collector has a diameter at least substantially half ofa diameter of the inner cathode.
 17. The method of claim 15, wherein theinner cathode and the cathode current collector are at leastsubstantially rectangular.
 18. The method of claim 11, wherein thecathode current collector is a conductive tube.
 19. The method of claim18, wherein the conductive tube comprises a conductive mesh.
 20. Themethod of claim 19, wherein the conductive tube comprises a perforatedmaterial.